CN110180598A - A kind of preparation method of efficiently heterogeneous electric Fenton magnetism wrapped film catalyst - Google Patents
A kind of preparation method of efficiently heterogeneous electric Fenton magnetism wrapped film catalyst Download PDFInfo
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- CN110180598A CN110180598A CN201910493313.8A CN201910493313A CN110180598A CN 110180598 A CN110180598 A CN 110180598A CN 201910493313 A CN201910493313 A CN 201910493313A CN 110180598 A CN110180598 A CN 110180598A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000005389 magnetism Effects 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 22
- METKIMKYRPQLGS-GFCCVEGCSA-N (R)-atenolol Chemical compound CC(C)NC[C@@H](O)COC1=CC=C(CC(N)=O)C=C1 METKIMKYRPQLGS-GFCCVEGCSA-N 0.000 claims description 12
- 229960002274 atenolol Drugs 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000004568 cement Substances 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 10
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 8
- 238000002386 leaching Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 hydroxyl radical free radical Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002876 beta blocker Substances 0.000 description 1
- 229940097320 beta blocking agent Drugs 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method of efficiently heterogeneous electric Fenton magnetism wrapped film catalyst, is related to electrochemical advanced oxidation heterogeneous catalysis technical field.Using Powdered Activated Carbon as catalyst carrier, magnetic active carbon carrier is prepared by chemical coprecipitation, then using hydroquinone as raw material, by the way that ferrous sulfate and hydrogen peroxide is added, poly- quinhydrones is obtained by series reaction and is coated on magnetic active carbon carrier surface, obtains magnetic wrapped film catalyst.Material requested of the present invention is cheap, synthesis technology is simple, coating slows down the loss of active component under acid condition, the catalyst effect of preparation is good, recoverable, the disadvantage that iron cement, catalyst recycling difficulty are also easy to produce in traditional Fenton's reaction is overcome, in terms of wastewater treatment with good application prospect.
Description
Technical field
The invention belongs to electrochemical advanced oxidation heterogeneous catalysis research and development technology fields, and in particular to a kind of efficiently non-equal
The mutually preparation method of electric Fenton magnetism wrapped film catalyst.
Background technique
Traditional Fenton-like system utilizes additional ferrous ion (Fe2+) with the H that adds2O2Reaction generates strong oxidizing property free radical
Carry out oxidation stain object, but hydrogen peroxide has unstability, decomposes in light, thus during transport and storage dangerous property,
The high requirements on the equipment.Homogeneous electro-fenton process is a kind of novel electrochemical oxidation technology, is referred under the action of extra electric field, is led to
A series of electrochemical reactions for crossing the generation of electrode material activity component generate H2O2And (or) Fe2+As persistently coming for Fenton reagent
Source, effect immediately generates the hydroxyl radical free radical of high activity, the method for oxygenolysis organic pollutants after the two generates.Electricity
Macromolecular, persistent organic pollutants in water can be degraded to the intermediate product of small molecule, easily biological-degradable by chemical oxidization method, directly
It is CO to permineralization2And H2O.But the deliquescent Fe in conventional homogeneous electricity Fenton-like system2+Easily iron cement is formed in pH > 3
And it is difficult to recycle, therefore heterogeneous electric Fenton technology becomes the research hotspot of electrochemical oxidation.It is urged by preparing solid
Agent avoids catalyst and is difficult to the shortcomings that recycling separation.
Active carbon (AC) has particularly preferred adsorption capacity due to its high-specific surface area, cellular structure and microstructure, can
Using as catalyst carrier, active carbon also has good acid and alkali resistance, often made extensively in sewage treatment as carrier
With.But active carbon powder be difficult from processing water phase in recycle separation, this not only influences handle effluent quality also result in powder live
Property charcoal turnover rate is very high.Magnetic ferriferous oxide is loaded the magnetic-particle application being prepared on the activated carbon by scholars at present
In water process, convenient for recycling while catalytic degradation.Ferriferous oxide energy catalyzing hydrogen peroxide (H2O2) generation hydroxyl free (
OH), and good catalytic effect is achieved.Recently, quinone has been used as redox mediator to carry out during contaminant degradation
Research, quinone, which is added, in the persulfate oxidation system can be improved the oxidation rate of pollutant, and quinone acts as " electronics wherein
The effect of shuttle " can promote electronics transfer to promote Fe3+/Fe2+Circulation.And there is no relevant report in electric Fenton-like system,
Therefore poly- quinhydrones coated catalysts, which are applied to electric Fenton-like system, has certain researching value.
In recent years, drug and personal care articles (PPCPs) are increasingly subject to the concern of people as a kind of emerging pollutant.Perhaps
More PPCPs components have stronger bioactivity, optical activity and polarity, are mostly existed in the environment with trace concentration.Beasts doctor
Medicine, agricultural medicine, the mankind take major way that medical and cosmetics uses are its importing environment.Wherein, atenolol
(ATL) it is used as a kind of beta-blocker drug, is widely used in treatment cardiovascular disease.And ATL has preferable water-soluble and antibiont
Degradability, conventional sewage processing method cannot be removed effectively.
Magnetic activity is prepared by chemical coprecipitation in carrier of the present invention using Powdered Activated Carbon as catalyst
Charcoal.Promote Fe using poly- quinhydrones (PHQ) " electron shuttle "3+/Fe2+Poly- quinhydrones is coated on magnetic by hydro-thermal method by the characteristics of circulation
Property activated carbon surface obtain magnetic wrapped film catalyst, applied this catalyst as heterogeneous catalysis in class electricity Fenton-like system
Catalytic degradation organic pollutant slows down the leaching of active component under acid condition while realizing efficient degradation.
Summary of the invention
The purpose of the present invention is intended to provide a kind of Preparation method and use of magnetic wrapped film catalyst, material requested of the present invention
Cheap, synthesis technology is simple, and the magnetic wrapped film catalyst of preparation is applied to electric Fenton-like system, and excellent catalytic effect has ring
Border close friend, slows down the advantages that loss of active component at recoverable, overcomes and is also easy to produce iron cement, catalysis in traditional Fenton's reaction
The difficult disadvantage of agent recycling.
Using Powdered Activated Carbon etc. as the carrier of catalyst in the present invention, magnetic work is prepared by chemical coprecipitation
Property high-area carbon AC/Fe3O4.Using hydroquinone as raw material, by the way that ferrous sulfate and hydrogen peroxide is added, obtained by series reaction
To poly- quinhydrones (PHQ) and it is coated on magnetic active carbon carrier surface, magnetic wrapped film catalyst is obtained, is denoted as PHQ/AC/Fe3O4。
The preparation step of magnetism wrapped film catalyst provided by the invention is as follows:
(1) iron chloride (FeCl is weighed in proportion3·6H2) and ferrous sulfate (FeSO O4·7H2O), it is added a certain amount of super
Pure water, the mechanical stirring in 50~80 DEG C of waters bath with thermostatic control is until be completely dissolved to obtain mixed liquor A.Fe2+With Fe3+Molar ratio be
(1~2): 2, preferably Fe2+With Fe3+Molar ratio 1.5:2；
(2) catalyst carrier is added in solution A, 0.5~1h of mechanical stirring, obtains mixed liquid B, catalyst carrier matter
Amount is 4:(11.5~15.3 with the ratio between iron chloride and ferrous sulfate gross mass), preferred mass ratio is 4:13.4；
(3) sodium hydroxide solution is slowly added dropwise into mixed solution B, stops being added dropwise when the pH of mixed liquor is 9；It is sufficiently anti-
It is staticly settled after answering 0.5~1h；It removes supernatant and uses ultrapure water repeated flushing sediment, be centrifugated and be placed in 80 DEG C true
Empty drying in oven obtains magnetic carrier, is denoted as AC/Fe3O4；
(4) hydroquinone is dissolved in ultrapure water, the magnetic carrier AC/Fe that step (3) obtain then is added3O4, mixing
0.5~1h obtains mixed liquor C.The mass ratio of magnetic catalyst carrier and hydroquinone is (1~2): (1~4), preferably 1:2；
(5) ferrous sulfate and hydrogen peroxide (30wt%) are added into mixed liquor C, is stirred 24 hours at 35 DEG C；Centrifugation
Solid product is collected, is washed with deionized, and is dry in 60 DEG C of vacuum drying oven, magnetic wrapped film catalyst is obtained, is denoted as
PHQ/AC/Fe3O4；Hydroquinone, ferrous sulfate, hydrogen peroxide mass ratio be (1.0~1.9): (0.003~0.012):
(1.85~7.4), preferred mass ratio are 1.6:0.006:3.7；
Catalyst carrier is selected from one or more such as active carbon powder, carbon nanotube, graphene, zeolites, preferably
The mesh number of active carbon powder is 100~400 mesh.
Application of the magnetic wrapped film catalyst that above-mentioned preparation method obtains in electric Fenton-like system difficult to degrade has for removing
Machine waste water, particularly for atenolol (ATL) waste water of degrading.
Compared with prior art, the present invention has following excellent effect:
1. preparation process is simple.Magnetism wrapped film catalyst production process of the present invention is easy, is not required to high temperature and pressure, reacts
Mild condition.
2. convenient for recycling.The magnetic wrapped film catalyst of preparation has stronger magnetism at solid-state form, can be in magnetic fields
Lower quick separating, convenient for recycling.
3. catalytic effect is obvious.Poly- quinhydrones accelerates electronics transfer, catalytic effect in the catalytic membrane that catalyst surface is formed
Significantly.
4. inactivation and leaching process that poly- quinhydrones coating slows down active component under acid condition.
Detailed description of the invention
Fig. 1 is the XRD diagram of the magnetic wrapped film catalyst of poly- quinhydrones cladding in embodiment 1.
Fig. 2 is the magnetic strength of the magnetic wrapped film catalyst of embodiment 1, external that magnetism can be realized in 30s with magnet attraction
The separation of wrapped film catalyst.
Fig. 3 is embodiment 1, the total iron ion leaching content of comparative example.
Fig. 4 is embodiment 1, embodiment 2, pollutant removal figure in comparative example.
Specific embodiment
It is illustrated in the following with reference to the drawings and specific embodiments, but the present invention is not limited to following embodiment.
Embodiment 1
(1) 7.8g iron chloride (FeCl is weighed for the ratio of 2:1.5 in molar ratio3·6H2) and 5.6g ferrous sulfate O
(FeSO4·7H2O) in beaker, 70mL ultrapure water is added, the mechanical stirring in 60 DEG C of waters bath with thermostatic control is until be completely dissolved to obtain
Mixed liquor A；
(2) 4g catalyst support powder active carbon (400 mesh) is added in solution A, 0.5~1h of mechanical stirring is obtained
Mixed liquid B；
(3) sodium hydroxide solution of 4mol/L is slowly added dropwise into mixed solution B, stops drop when the pH of mixed liquor is 9
Add.It is staticly settled after sufficiently 0.5~1h of reaction；Remove supernatant and use ultrapure water repeated flushing sediment, centrifuge separation juxtaposition
Magnetic active carbon carrier is finally obtained in drying in 80 DEG C of vacuum drying oven, is denoted as AC/Fe3O4；
(4) 1.6g hydroquinone is dissolved in 140mL ultrapure water, 0.8g magnetic active carbon carrier AC/ is then added
Fe3O4, the mass ratio of magnetic active carbon carrier and hydroquinone is 1:2, mixes 0.5~1h, obtains mixed liquor C；
(5) 6mg ferrous sulfate and 3.7g hydrogen peroxide (30wt%) are added into mixed liquor C, it is small that 24 are stirred at 35 DEG C
When.Solid product is collected by centrifugation, is washed with deionized, and is dry in 60 DEG C of vacuum drying oven, obtains magnetic coating catalysis
Agent is denoted as PHQ/AC/Fe3O4.The XRD diagram of prepared magnetic wrapped film catalyst as shown in Figure 1, be 30.1,35.4 in 2 θ,
Occur (200) at 43.1,56.9 and 62.5 respectively, (311), (400), the characteristic peak of (511) and (400) is determined as Fe3O4
Crystal structure.The recycling ability of magnetic wrapped film catalyst is as shown in Fig. 2, external can realize magnetism with magnet attraction in 30s
The separation of wrapped film catalyst.
The magnetic wrapped film catalyst of above-mentioned preparation is applied to atenolol waste water of degrading in heterogeneous electric Fenton-like system.With
The graphite felt of 5 × 6cm is as cathode, and using 1 × 5cm platinized platinum as anode, atenolol initial concentration is 20mg/L, 0.05M's
For sodium sulphate as electrolyte, it is 100mg/L that catalyst, which adds concentration, and the constant current that system applies is 90mA, pH value of solution 3.Instead
Process is answered to be aerated (0.9L/min) always, preceding 40min is the suction-operated of catalyst, and the heterogeneous electricity of the building that is powered when 40min is fragrant
System.Suction-operated removal 6%, when energization 60min, the degradation of atenolol reaches 100%.Total iron ion leaching content is as schemed
Shown in 3.Removal rate is as shown in Figure 4.
Embodiment 2
The present embodiment and 1 preparation process of embodiment are the difference is that be added magnetic active carbon and to benzene two in step (4)
The mass ratio of phenol is 1:4.The magnetic wrapped film catalyst of above-mentioned preparation is applied to Ah Ti Lip river of degrading in heterogeneous electric Fenton-like system
That waste water, treatment conditions are the same as embodiment 1, preceding 40min suction-operated removal about 5%, energization 120min, the degradation rate of atenolol
It is 98%.Removal rate is as shown in Figure 4.
Comparative example
This comparative example is not difference from example 1 is that AC/Fe3O4Carry out coating processing.It will obtain magnetic activity
High-area carbon AC/Fe3O4Applied to atenolol waste water of degrading in heterogeneous electric Fenton-like system, treatment conditions are preceding with embodiment 1
40min suction-operated removal rate 34%, energization 120min, the degradation rate of atenolol are 92%.Total iron ion leaching content such as Fig. 3
It is shown.Removal rate is as shown in Figure 4.
Embodiment and comparative example the result shows that, although the presence of poly- quinhydrones catalytic membrane largely slows down catalyst
The catalytic effect of catalyst is still greatly strengthened to the suction-operated of pollutant, it is known that poly- quinhydrones promotes Fe3+/Fe2+It follows
Ring, but when poly- quinhydrones amount is excessive, the catalytic effect risen is less obvious, it is seen that quinone promotes electronics transfer, and there are optimum conditions.
With non-coating magnetic active carbon carrier AC/Fe3O4It compares, poly- quinhydrones coats the magnetic wrapped film catalyst PHQ/AC/ being prepared
Fe3O4The leaching of total iron ion in acid condition is slowed down to a certain extent.
Claims (9)
1. a kind of preparation method of efficiently heterogeneous electric Fenton magnetism wrapped film catalyst, which is characterized in that specifically include following step
It is rapid:
Preparation step is as follows:
(1) iron chloride (FeCl is weighed in proportion3·6H2) and ferrous sulfate (FeSO O4·7H2O), a certain amount of ultrapure water is added,
The mechanical stirring in 50~80 DEG C of waters bath with thermostatic control is until be completely dissolved to obtain mixed liquor A；
(2) catalyst carrier is added in solution A, 0.5~1h of mechanical stirring obtains mixed liquid B；
(3) sodium hydroxide solution is slowly added dropwise into mixed solution B, stops being added dropwise when the pH of mixed liquor is 9；Sufficiently reaction
It is staticly settled after 0.5~1h；It removes supernatant and uses ultrapure water repeated flushing sediment, be centrifugated and be placed in 80 DEG C of vacuum
Drying in oven obtains magnetic carrier, is denoted as AC/Fe3O4；
(4) hydroquinone is dissolved in ultrapure water, the magnetic carrier AC/Fe that step (3) obtain then is added3O4, mixing 0.5
~1h obtains mixed liquor C；
(5) ferrous sulfate and hydrogen peroxide are added into mixed liquor C, is stirred 24 hours at 35 DEG C；Solid product is collected by centrifugation, uses
Deionized water washing, and it is dry, magnetic wrapped film catalyst is obtained, PHQ/AC/Fe is denoted as3O4。
2. a kind of preparation method of efficiently heterogeneous electric Fenton magnetism wrapped film catalyst described in accordance with the claim 1, feature
It is, step (1) Fe2+With Fe3+Molar ratio be (1~2): 2, preferably Fe2+With Fe3+Molar ratio 1.5:2.
3. a kind of preparation method of efficiently heterogeneous electric Fenton magnetism wrapped film catalyst described in accordance with the claim 1, feature
It is, catalyst carrier quality and the ratio between iron chloride and ferrous sulfate gross mass are 4:(11.5~15.3 in step (2)), preferably
Mass ratio is 4:13.4.
4. a kind of preparation method of efficiently heterogeneous electric Fenton magnetism wrapped film catalyst described in accordance with the claim 1, feature
It is, catalyst carrier is selected from active carbon powder, carbon nanotube, graphene, zeolite one or more, preferably active powdered carbon
The mesh number at end is 100~400 mesh.
5. a kind of preparation method of efficiently heterogeneous electric Fenton magnetism wrapped film catalyst described in accordance with the claim 1, feature
It is, the mass ratio of step (4) magnetic active carbon carrier and hydroquinone is (1~2): (1~4), preferably 1:2.
6. a kind of preparation method of efficiently heterogeneous electric Fenton magnetism wrapped film catalyst described in accordance with the claim 1, feature
Be, hydroquinone in step (5), ferrous sulfate, hydrogen peroxide mass ratio be (1.0~1.9): (0.003~0.012):
(1.85~7.4), preferred mass ratio are 1.6:0.006:3.7.
7. the magnetic wrapped film catalyst being prepared according to method described in any one of claims 1-6.
8. the magnetic wrapped film catalyst being prepared according to method described in any one of claims 1-6 is in electric Fenton-like system
Using for removing organic wastewater with difficult degradation thereby.
9. according to the application of claim 8, for atenolol of degrading (ATL) waste water.
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